Crossed McMurry Coupling Reactions for Porphycenic Macrocycles: Non-Statistical Selectivity and Rationalisation
Thomas Y Cowie1, Lorna Kennedy1, Justyna M Żurek1
1School of EPS - Institute of Chemical Sciences, Heriot-Watt University Riccarton, Edinburgh, EH14 4AS, UK E-mail: m.j.paterson@hw.ac.uk m.w.p.bebbington@hw.ac.uk http://www.theophotochem.eps.hw.ac.uk/Home.html , http://www.hw.ac.uk/schools/engineering-physical-sciences/staff-directory/mb.htm.
None:
Crossed McMurry reactions of bifuran- or bithiophenedicarbaldehydes with bipyrroledicarbaldehydes have been studied for the first time. Only those porphycenic macrocycles derived from homocoupled McMurry products were formed. The results are explained by using both density functional theory and electron propagator computations to model the electron affinity of the dialdehyde starting materials. It was predicted that bifuran\bithiophene cross-coupling would indeed occur, and this was demonstrated by the first synthesis of a novel dioxa,dithio hetero-porphycenoid annulene. This approach will allow the prior identification of viable substrates for related crossed McMurry reactions.
Related Concept Videos
Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction
Pericyclic Reactions: Introduction
Pericyclic reactions can be classified into three categories: electrocyclic reactions, cycloaddition reactions, and sigmatropic rearrangements. Electrocyclic reactions and sigmatropic...
Cycloaddition Reactions: MO Requirements for Thermal Activation
Cycloaddition Reactions: Overview
Woodward–Hoffmann Selection Rules and Microscopic Reversibility
Thermal and Photochemical Electrocyclic Reactions: Overview
![Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-phosphinetriyltripiperidine]}palladium Under Mild Reaction Conditions](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F51444.jpg&w=3840&q=50)

![Cercosporin-Photocatalyzed [4+1]- and [4+2]-Annulations of Azoalkenes Under Mild Conditions](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F60786.jpg&w=3840&q=50)